Herbicidal 4-trifluoromethyl-4-nitrodiphenyl ethers

ABSTRACT

Compounds of the formula:   &lt;IMAGE&gt;   wherein X is hydrogen, halo, trihalomethyl, alkyl, or cyano; Y is hydrogen or halo; and Z is a hydroxy substituted alkyl group and compositions containing these compounds exhibit herbicidal activity.

THE DISCLOSURE

This is a continuation-in-part of Ser. No. 926,355 filed July 20, 1978, now abandoned which is of C-I-P of application Ser. No. 808,415 filed June 20, 1977 now U.S. Pat. No. 4,185,995 which is a division of application Ser. No. 617,562, filed Sept. 29, 1975, now U.S. Pat. No. 4,046,798 granted Sept. 6, 1977, which is in turn a division of Ser. No. 331,719, filed Feb. 12, 1973 now U.S. Pat. No. 3,928,416, granted Dec. 23, 1975, which is in turn a continuation-in-part of Ser. No. 234,651, filed Mar. 14, 1972 now U.S. Pat. No. 3,798,276, granted Mar. 19, 1974.

This invention relate to nitrodiphenyl ethers, compositions containing nitrodiphenyl ethers and methods of controlling weeds.

Diphenyl ethers are known to be effective weed control agents. See for example; U.S. Pat. Nos. 3,928,416; 3,454,392; 3,798,276; 3,873,303; 4,001,005; and 4,029,493 among the many patents issued. However, even now herbicidal effectiveness of a diphenyl ether cannot be predicted knowing only the structure and often quite closely related compounds will have quite differentweed control abilities. See, Advances in Agronomy, Vol. 24, pages 331, 332, 355, 356, 357 and 358, Herbicides, Chemical Degradation and Mode of Action, Kearney and Kaufman, Vol. 2, Dekker, Inc. pages 552-563 and 728-737 and Mode of Action of Herbicides, Ashton and Crafts and, also, U.S. Pat. Nos. 3,454,392 and 3,776,961.

An ideal herbicide should give selective weed control over the full growing season, with a single administration at low rates of application. It should be able to control all common weeds by killing them as the seed, the germinating seed, the seedling, and the growing plant. At the same time, the herbicide should be substantially non-phytotoxic to the crops to which it is applied and should decompose or otherwise be dissipated so as not to poison the soil permanently. The known diphenyl ether herbicides fall short of these ideals and thus the search continues to discover new herbicides which are more selective or which complement the known diphenyl ethers.

In accordance with the present invention, there is provided a class of diphenyl ethers having the formula: ##STR2## wherein X is hydrogen, halo, such as, chloro, fluoro, bromo, iodo and the like, preferably, fluoro or chloro; trihalomethyl, preferably trifluoromethyl; or (C₁ -C₄) alkyl such as methyl, ethyl, propyl, butyl and the like, preferably, methyl or cyano;

Y is hydrogen or halo, such as, bromo, chloro, fluoro, iodo and the like, preferably, fluoro or chloro and Z is hydroxy substituted alkyl group preferably an alkyl group having 1 to 4 carbon atoms.

Particular preferred compounds of the invention are those wherein Y is hydrogen; X is chloro and Z is hydroxymethyl or hydroxyethyl.

The diphenyl ethers (I, supra) of the invention are useful as preemergence and postemergence herbicides. Preemergence herbicides are ordinarily used to treat the soil by application either before seeding, during seeding, or after seeding and before the crop emerges.

Postemergence herbicides are those which are applied after the plants have emerged and during their growth period. The compounds of this invention are especially active as postemergence herbicides.

Among the crops on which the diphenyl ethers of the invention can be advantageously employed are, cotton, soybeans, peanuts, beans, peas, carrots, corn, wheat and other cereal crops.

The diphenyl ethers (I, supra) are useful for controlling weeds in rice crops. When used in transplanted rice crops, the ethers can be applied either preemergence or postemergence to weeds--that is, they can be applied to the transplanted rice plants and their growth medium either before the weed plants have emerged or while they are in their early stages of growth. The ethers can be applied to the growth medium either before or after the rice has been transplanted to that medium.

The diphenyl ethers (I, supra) can be applied in any amount which will give the required control of weeds. A standard rate of application ofthe herbicides of the invention is in the range from about 0.02 to about 12 pounds of diphenyl ether per acre. A preferred range is from about 0.1 to about 2 pounds per acre.

Under some conditions, the diphenyl ethers (I, supra) may be advantageously incorporated into the soil or other growth medium prior to planting a crop. This incorporation can be by any convenient means, including simple mixing with the soil, applying the diphenyl ether to the surface of the soil and then disking or dragging into the soil to the desired depth, or by employing a liquid carrier.

The diphenyl ethers of the invention can be applied to the growth medium or to plants to be treated either neat or as a component in a herbicidal composition or formulation which also comprises an agronomically acceptable carrier. "Agronomically acceptable carrier" is any carrier which can be used to dissolve, disperse or diffuse a herbicidal compound in the composition without impairing the effectiveness of the herbicidal compound and which by itself has no permanent detrimental effect on the soil, equipment, crops, or agronomic environment. Mixtures of the diphenyl ethers of the invention may also be used in any of these herbicidal formulations. The herbicical compositions of the invention can be either solid or liquid formulations or solutions. For example, the diphenyl ethers can be formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated.

It is usually desirable, particularly in post-emergence applications, to include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers, adhesives, and the like, in accordance with agricultural practices. Examples of adjuvants which are commonly used in the art can be found in the John W. McCutcheon, Inc. publication "Detergents and Emulsifiers 1969 Annual."

Examples of solvents which are useful in the practice of this invention include alcohols, ketones, aromatic hydrocarbons, dimethyl formamide, dioxane, dimethyl sulfoxide, and the like. Mixtures of these solvents can also be employed. The concentration of the solution can vary from about 2% to about 98% of active product with a preferred range being from about 25% to about 75%.

For the preparation of emulsifiable concentrates, the diphenyl ether can be dissolved in organic solvents, such as toluene, xylene, methylated naphthalene, corn oil, pine ol, isophorone, cyclohexanone, methyl oleate, and the like, or in mixtures of these solvents, together with an emulsifying agent which permits dispersion in water. Suitable emulsifiers include, ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids, and reactive amines and partially esterified polyhydric alcohols. Solvent-soluble sulfates or sulfonates, such as the alkaline earth salts or amine salts or alkylbenzene-sulfonates and the fatty alcohol sodium sulfates, having surface-active properties can be used as emulsifiers either alone or in conjunction with an ethylene oxide reaction product. Flowable concentrates are formulated similarly to the emulsifiable concentrates and include, in addition to the above components, water and a stabilizing agent such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentration of the active ingredient in emulsifiable concentrates is usually from about 10% to 60% and in flowable emulsion concentrates, can be as high as about 75%.

Wettable powders suitable for spraying, can be prepared by admixing the compound with a finely divided solid, such as clays, inorganic silicates and carbonates, and silicas and then incorporating wetting agents, sticking agents, and/or dispersing agents. The concentration of active ingredients in such formulations is usually in the range of from about 20% to about 98%, and, preferrably, from about 40% to about 75%. A dispersing agent can constitute about 0.5% to about 3% of the composition, and a wetting agent can constitute from about 0.1% to about 5% of the composition.

Dusts can be prepared by mixing the compounds of the invention with finely divided inert solids which may be organic or inorganic in nature. Materials useful for this purpose include, for example, botanical flours, silicas, silicates, carbonates and clays. One convenient method of preparing a dust is to dilute a wettable powder with a finely divided carrier. Dust concentrates containing from about 20% to about 80% of the active ingredient are commonly made and are subsequently diluted from about 1% to about 10% use concentration.

Granular formulations can be prepared by impregnating a solid, such as granular fuller's earth, vermiculite, ground corn cobs, seed hulls, including bran or other grain-hulls, or similar material. A solution of one or more of the diphenyl ethers in a volatile organic solvent can be sprayed or mixed with the granular solid and the solvent then removed by evaporation. The granular material can have any suitable size, with a preferable size in the range of from about 16 to 60 mesh. The diphenyl ether will usually comprise from about 2 to about 15% of the granular formulation.

The diphenyl ethers of the invention can also be mixed with fertilizers or fertilizing materials before their application. In one type of solid fertilizing composition in which the diphenyl ethers can be used, particles of a fertilizer or fertilizing ingredients, such as ammonium sulfate, ammonium nitrate, or ammonium phosphate, can be coated with one or more of the ethers. The solid diphenyl ethers and solid fertilizing material can also be admixed in mixing or blending equipment, or they can be incorporated with fertilizers in granular formulations. Any relative proportion of diphenyl ether and fertilizer can be used which is suitable for the crops and weeds to be treated. The diphenyl ether will commonly be from about 5% to about 25% of the fertilizing composition. These compositions provide fertilizing materials which promote the rapid growth of desired plants, and at the same time control the growth of undesired plants.

The diphenyl ethers of the invention can be applied as herbicidal sprays by methods commonly employed, such as conventional high-gallonage hydraulic sprays, low-gallonage sprays, airblast spray, aerial sprays and dusts. For low volume applications a solution of the compound is usually used. The dilution and rate of application will usually depend upon such factors as the type of equipment employed, the method of application, the area to be treated and the type and stage of development of the weeds.

For some applications, it may be desirable to add one or more different herbicides along with diphenyl ethers of the invention. Examples of other herbicides which can be incorporated to provide additional advantages and effectiveness include:

Carboxylic Acids and Salts and Ester Derivatives Thereof

2,3,6-trichlorobenzoic acid, 2,3,5,6-tetrachlorobenzoic acid, 2-methoxy-3,5,6-trichlorobenzoic acid, 2-methoxy-3,6-dichlorobenzoic acid, 2-methyl-3,6-dichlorobenzoic acid, 2,3-dichloro-6-methylbenzoic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, 2-(2,4,5-trichlorophenoxy) propionic acid, 4-(2,4-dichlorophenoxy) butyric acid, 4-(2-methyl-4-chlorophenoxy) butyric acid, 2,3,6-trichlorophenylacetic acid, 3,6-endoxohexahydrophthalic acid, dimethyl 2,3,5,6-tetrachloroterephthalate, trichloroacetic acid, 2,2-dichloropropionic acid, 3-amino-2,5-dichlorobenzoic acid, 2,3-dichloroisobutyric acid.

Carbamic Acid Derivatives

ethyl N,N-Di(n-propyl thiocarbamate, propyl N,N-di-(n-propyl) thiocarbamate, ethyl N-ethyl-N-(n -butyl) thiocarbamate, ethyl N-ethyl-N-(n-butyl)thiocarbamate, propyl N-ethyl-N-(n-butyl)thiocarbamate, 2-chloroallyl N,N-diethyldithiocarbamate, N-methyldithiocarbamic acid salts, ethyl 1-hexamethyleneiminecarbothiolate, isopropyl N-phenylcarbamate, isopropyl N-(m-chlorophenyl)carbamate, 4-chloro-2-butynyl N-(m-chlorophenyl carbamate, methyl N-(3,4dichlorophenyl) carbamate, methyl m-hydroxcarbanilate-m-methylcarbanilate, S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate.

Phenols

dinitro-o-(sec-butyl)phenol and its salts, pentachlorophenol and its salts

Substituted Ureas

3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-3-methoxy-1,1-dimethylurea, 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1-n-butyl-1-methylurea, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, 3-(4-chlorophenyl)-1-methoxy-1-methylurea, 3-(3,4-dichlorophenyl)-1,1,3-trimethylurea, 3-(3,4-dichlorophenyl)-1,1-diethylurea, dichloral urea, N'[4-[2-p-methylphenyl)ethoxy]phenyl]-N-methoxy-N-methylurea,1,1,3-trimethyl-3-(5-p-chlorobenzylthio-1,3,4-thiadiazol-2-yl)urea, 3-[p-chlorophenoxy)phenyl]-1,1-dimethylurea.

Substituted Triazines

2-chloro-4,6-bis(ethylamino)-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis(methoxypropylamino)-s-triazine, 2-methoxy-4,6-bis-(isopropylamino)-s-triazine, 2-chloro-4-ethylamino-6-(3-methoxypropylamino)-s-triazine, 2-methylmercapto-4,6-bis-(ethylamino)-s-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis(isopropylamino)-s-triazine, 2-methoxy-4,6-bis(ethylamino)-s-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine, 2-methylmercapto-4-(2-methoxyethylamino)-6-isopropylamino-s-triazine.

Diphenyl Ether Derivatives

2,4-dichloro-4'-nitrodiphenyl ether, 2,4,6-trichloro-4'-nitrodiphenyl ether, 2,4-dichloro-6-fluoro-4'-nitrodiphenyl ether, 2-chloro-4trifluoromethyl-3'-carboxy-4'-nitrodiphenylether and its salt and ester derivatives, 3-methyl-4'-nitrodiphenyl ether, 3,5-dimethyl-4'-nitrodiphenyl ether, 2,4'-dinitro-4-trifluoromethyldiphenyl ether, 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether, sodium 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate.

Anilides

N-(3,4-dichlorophenyl)propionamide, N-(3,4-dichlorophenyl) methacrylamide, N-(3-chloro-4-methylphenyl)-2-methylpentaamide, N-(3,4-dichlorophenyl)trimethylacetamide, N-(3,4-dichlorophenyl) β,β-dimethylvaleramide, N-isopropyl-N-phenylchloroacetamide, N-n-butoxymethyl-N-(2,6-diethylphenyl)chloroacetamide and N-n-methoxymethyl-N-(2,6-diethylphenyl)chloroacetamide, 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide.

Uracils

5-bromo-3-s-butyl-6-methyluracil, 5-bromo-3-cyclohexyl-1,6-dimethyluracil, 3-cyclohexyl-5,6-trimethyleneuracil, 5-bromo-3-isopropyl-6-methyluracil and 3-tert-butyl-5-chloro-6-methyluracil.

Nitriles

2,6-dichlorobenzonitrile, diphenylacetonitrile, 3,5-dibromo-4-hydroxybenzonitrile, and 3,5-diiodo-4-hydroxybenzonitrile.

Other Organic Herbicides

2-chloro-N,N-diallylacetamide, N-(1,1-dimethyl-2-propynyl)-3,5-dichlorobenzamide, maleic hydrazide, 3-amino-1,2,4-triazole, monosodium methanearsonate, N,N-dially-2-chloroacetamide, disodium methanearsonate, N,N-dimethyl-β,β-diphenylacetamide, N,N-di(n-propyl-2,6-dinitro-4-trifluoromethylaniline, N,N-di(n-propyl)-2,6-dinitro-4-methylaniline, N,N-di(n-propyl)-2,6-dinitro-4-methylsulfonylaniline, N³,N³ -di-n-propyl-2,4-dinitro-6-trifluoromethyl-m-phenylenediamine, 3,5-dinitro-N⁴,N⁴ -dipropylsulfanilamide, 4-isopropyl-2,6-dinitro-N,N-dipropylaniline, N-(2-chloroethyl)-2,6-dinitro-N-propyl-4-trifluoromethylaniline, O-(2,4-dichlorophenyl)-O-methylisopropylphosphoramidothioate, 4-amino-3,5,6-trichloropicolinic acid, 2,3-dichloro-1,4-naphthoquinone, di-(methoxythiocarbonyl)disulfide, 3-isopropyl-1H-2,1,3-benzothiadiazine(4)3H-one-2,2,dioxide, 6,7-dihydrodipyridol-[1,2-a:2',1'-c]pyrazidinium salts, 1,1'-dimethyl-4,4'bi-pyridinium salts and 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine, 2-α-napthoxy)-N-diethylacetamide, 2-N-(1-napthylaminocarbonyl)benzoic acid, 3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide, methyl-2-[4-(4chlorophenoxy)phenoxy]propionate, methyl-2-[4-(3,5-dichloropyrid-2-yl)phenoxy]propionate, 2-[1-(allyloxyamino)propylidene]4-carbomethoxy-5,5-dimethylcylohexane-1,3-dione.

When mixtures of herbicides are employed, the relative proportions which are used will depend upon the crop to be treated and the degree of selectivity in weed control desired.

The diphenyl ethers of the invention or their precursors can be prepared by reacting a suitably substituted phenol, or the potassium or sodium salt of the phenol, with a suitably substituted halobenzene, such as a chloro- or fluorobenzene, in the presence of an alkaline agent.

Synthesis

Carbinols of the invention may be prepared from the corresponding esters or other acid derivatives, or ketones, by reduction, for example with metal hydrides, or from the aldehyde by reaction with metal alkyl, e.g. an alkyl lithium, or Grignard reagent. They may also be prepared from the corresponding alkylbenzene either directly, by controlled oxidation, or by controlled monohalogenation followed by hydrolysis. Nitration will take place either before or after construction of the side chain.

Alternatively, the side chain may be introduced before construction of the diphenylether.

The following examples will further illustrate this invention but are not intended to limit it in any way.

EXAMPLE 1 2-Chloro-4-trifluoromethyl-3'-hydroxymethyl-4'-nitrodiphenyl ether

A solution of 2-chloro-4-trifluoromethyl-3'-carbomethoxy-4'nitrodiphenyl ether (1.5 g) in tetrahydrofuran (20 ml) at -10° C. is treated with lithium aluminum hydride (400 mg) added in one lot. The reaction exotherms to 10° C. and after 60 seconds is quenched by pouring onto ice/water. This reaction is repeated five times and the combined products diluted with ether, washed with water, dried, stripped, filtered through silica gel in 50% benzene/hexane, stripped and recrystallized from hexane to afford 2-chloro-4-trifluoromethyl-3-hydroxymethyl nitrodiphenyl ethers (3 g) m.p. 88°-91° C.

In Table I, typical diphenyl ethers of the invention are listed with their melting points and elemental analysis.

                                      TABLE I                                      __________________________________________________________________________     Elemental Analysis                                                             Example               % C    % H                                                                               % N                                                                               % Cl                                                                               % F                                     __________________________________________________________________________     1.   CH.sub.2 OH                                                                            C.sub.14 H.sub.9 ClF.sub.3 NO.sub.4                                                     Found 48.39                                                                           2.62                                                                              3.78                                                                              10.34                                                                              15.8                                         m.p. 88-91° C.                                                                           Calc. 48.36                                                                           2.61                                                                              4.03                                                                              10.20                                                                              16.3                                    2.   CH.sub.2 OEt                                                                           C.sub.16 H.sub.13 ClF.sub.3 NO.sub.4                                                    Found 51.40                                                                           3.59                                                                              3.34                                                                              9.63                                                                               --                                           oil              Calc. 51.1                                                                            3.5                                                                               3.7                                                                               9.4 --                                      __________________________________________________________________________

One skilled in the art will appreciate that the above examples are merely illustrative and are capable of a wide variation and modification without departing from the spirit of this invention as defined by the following claims.

Test Procedure

This example shows the herbicidal activity of the diphenyl ethers of the invention exhibited on the following representative species:

    ______________________________________                                                                  Approx.                                                                        No. Seeds                                             ______________________________________                                         Monocots:                                                                              Barnyardgrass                                                                              (Echinochloa   25                                                              crusgalli)                                                         Downybrome  (Bromus tectorum)                                                                             20                                                  Foxtail     (Setaria spp)  25                                                  Johnsongrass                                                                               (Sorghum Halepense)                                                                           25                                                  Nutsedge    (Cyperus       5                                                               esculentus)                                                        Wild Oat    (Avena fatua)  20                                          Dicots: Cocklebur   (Xanthium pensyl-                                                                             3                                                               vanicum)                                                           Marigold    (Tagetes spp)  15                                                  Morning Glory                                                                              (Ipomoea spp)  10                                                  Tomato      (Lycopersicon  15                                                              esculentum)                                                        Velvetleaf  (Abutilon      15                                                              theophrasti)                                               ______________________________________                                    

The following test procedure is employed. Seeds of the above species are planted in soil in trays (approx. 7"×101/2×3"). For preemergence tests, the trays are sprayed with the test compound immediately after planting. For postemergence tests, the seeds are allowed to germinate and after growing in the greenhouse for two weeks, the growing plants are treated with the test compound. The compound to be evaluated is dissolved in acetone or water and sprayed over the trays using a carrier volume equivalent to 50 gallons per acre at the rate of application (in pounds per acre, lb/A) specified in the table. About two weeks after application of the test compound, the state of growth of the plants is observed and the phytotoxic effect of each compound determined as follows: each species is evaluated on a scale of 0-100 in which 0=no activity and 100=total kill and the results for the monocots and dicots separately averaged. The following table shows the results obtained for the compounds of the invention at 2 lb/A. and 4 lb/A.

                                      TABLE II                                     __________________________________________________________________________     Biological Data                                                                          MONOCOTS                  DICOTS                                               Barnyard-    Green                                                                              Yellow                                                                              Wild                Morning                    Compound                                                                             lbs/A                                                                              grass Downybrome                                                                            Foxtail                                                                            Nutsedge                                                                            Oats                                                                               Cocklebur                                                                            Marigold                                                                            Tomato                                                                              Glory                                                                               Velvetleaf            __________________________________________________________________________     Ex. 1 Pre 2                                                                              80    0      100 0    0   0     0    0    0    70                          Post 4                                                                             30    0      30  0    20  0     20   30   50   70                    Ex. 2 Pre 2                                                                              20    0      90  0    0   --    50   0    10   100                         Pre 4                                                                              95    60     100 0    30  --    95   75   80   100                         Post 2                                                                             0     0      10  0    20  10    0    0    10   70                          Post 4                                                                             0     0      10  0    0   0     40   50   20   20                    __________________________________________________________________________ 

We claim:
 1. A compound of the formula: ##STR3## wherein X is hydrogen, halo, trifluoromethyl, (C₁ -C₄) alkyl, or Y is hydrogen, halo or trifluoromethyl; and Z is hydroxy substituted (C₁ -C₄) alkyl group.
 2. A method of controlling weeds which comprises applying to the surface of the growth medium prior to the emergence of the weeds from the growth medium a compound according to claim 1 in an amount sufficient to control the growth of the weeds.
 3. The method of claim 3 wherein the compound is applied at a rate of about 0.1 to about 12 pounds per acre.
 4. A method of controlling weeds which comprises applying to weed seedlings a compound according to claim 1 in an amount sufficient to control the growth of the seedlings.
 5. The method of claim 4 wherein the compound is applied at a rate of about 0.1 to about 12 pounds per acre.
 6. A herbicidal composition comprising a compound according to claim 1 and an agronomically acceptable carrier.
 7. A composition according to claim 6 wherein the carrier is an organic solvent.
 8. A composition according to claim 6 which also comprises a surfactant. 